Substituted sulfonyl triazines

ABSTRACT

Sulfonamide compounds of the formula   WHEREIN Y and Y&#39;&#39; are members selected from the group consisting of   WHEREIN R1 and R2 are members selected from the group consisting of hydrogen and lower alkyl, and X is the conjugate base of a Lowry-Bronsted acid which has a dissociation constant in water of between 5 X 10 2 and 5 X 10 5. These compounds can be used for reaction with active hydrogen containing polymeric material such as for the treatment of cellulosic textiles.

nited States Patent [1 1 Tesoro et al.

m1 3,7MA73 [451 Sept. 25, 11973 SUBSTITUTED SULFONYL TRIAZINES [75] Inventors: Giuliana C. Tesoro, Dobbs Ferry,

N.Y.; Richard N. Ring, Woodridge, NJ.

[73] Assignee: J. P. Stevens & Co., Inc., New York,

[22] Filed: July 23, 1970 [21] Appl. No.: 63,990

[52] US. Cl. 260/248 NS, 106/176, 260/88.3 R

Primary Examiner-John M. Ford Att0rnyBrowne, Beveridge and DeGrandi [57] ABSTRACT Sulfonamide compounds of the formula CH2 YSOzlTI NSOZY' wherein Y and Y are members selected from the group consisting of wherein R and R are members selected from the group consisting of hydrogen and lower alkyl, and

X is the conjugate base of a Lowry-Bronsted acid which has a dissociation constant in water of between 5 X10 and 5 X 10? These compounds can be used for reaction with active hydrogen containing polymeric material such as for the treatment of cellulosic textiles.

2 Claims, N0 Drawings 1 SUBSTITUTED SULFON YL TRIAZINES The present application is a division of U.S. Pat. application Ser. No. 656,613 filed June 12, 1967, now U.S. Pat. No. 3,539,571; which is a divisional of U.S. Pat. application Ser. No. 337,997 filed Jan. 16, 1964 now abandoned.

The present invention relates to sulfonamide compounds and methods of making them, and more particularly to sulfonamide compounds that are particularly valuable for the chemical modification of polymers containing active hydrogen atoms, as crosslinking agents for cellulosic polymers, as intermediates for chemical synthesis and for the preparation of therapeutic substances.

Sulfonamide compounds of the present invention are characterized by the presence of at least one functional group that is capable of reacting with the active hydrogen atoms of various polymeric materials as well as acting as sites for polymerization and as centers of therapeutic activity.

Accordingly, it is an object of the present invention to provide sulfonamide compounds containing at least one reactive functional group.

it is a further object of the present invention to provide reactive sulfonamide compounds capable of reacting with active hydrogen containing polymeric materials for the chemical modification thereof.

It is a further object of the present invention to provide symmetrical and unsymmetrical polyfunctional sulfonamide compounds.

It is a further object of the present invention to provide methods for making certain sulfonamide compounds that can be employed for the modification of active hydrogen-containing polymeric materials.

In attaining the above objects, one feature of the present invention resides in certain novel sulfonamide compounds which contain at least one terminal group capable of reaction with the active hydrogen atoms of various polymeric materials in general, and in particular with the hydroxyl groups of cellulosic textile materials.

Another feature of the present invention resides in certain sulfonamide compounds which contain at least two reactive terminal groups.

Other objects, features and advantages of the present invention will become apparent from the following detailed description thereof.

The sulfonamide compounds of the present invention are characterized in that they contain at least one reactive terminal group of the formula:

More particularly, the sulfonamide compounds of the present invention may be represented by the formulae:

and

ll. YSO- N() wherein Y is selected from the group consisting of itII-(]', l ;()(|ll(|ll and xvii-(HF l it, In in in R1 wherein R is a member selected from the group consisting of hydrogen and lower alkyl groups,

R, is a member selected from the group consisting of hydrogen and lower alkyl,

X is the conjugate base of a Lowry-Bronsted acid which has a dissociation constant in waterbetween 5 X 10 and 5 X 10 wherein Y and Y are members selected from the group consisting of R1CII(1, R1O('?II(|JII and XC1I(|3II wherein R is a member selected from the group consisting of hydrogen and lower alkyl; i.e., one to five carbon atoms,

R is a member selected from the group consisting of hydrogen and lower alkyl,

X is the conjugate base of a Lowry-Bronsted acid which has a dissociation constant in water between 5 X 10 and 5X 10 R is a member selected from the group consisting of hydrogen, lower alkyl from one to five carbon atoms, hydroxyalkyl, e.g. -CH,OH, -CH CH OH, and alkoxy alkyl, e.g. -CH OCH -CH CH OC,H and Z is a divalent aliphatic or alicyclic group and is selected from the group consisting of alkylene groups of the formula:

-CnHZn wherein n is an integer with a value of 1 to 10,

polyoxyethylene groups of the formula:

wherein m is an integer with a value of l to 20, polyoxypropylene groups with theformula:

ici n rusin which m is an integer with a valve of 1 to 20, and Y hydroxyalkylene groups of the formula:

wherein n has a value of 3 to 10 and x has a value of l to 4, e.g.

Heterocyclic compounds represented by Formula ll above include compounds represented by the structural formula YSOzN wherein Y and Y have the meaning given above.

Unsymmetrical polyfunctional compounds which come within the Formula I can be represented by the structural formula: VI.

wherein Y, R and R have the meanings previously given above.

In these compounds the N-methylol grouping -CH,;OR is capable of reaction with active hydrogencontaining polymers under certain conditions while the reactive grouping Y as defined above will react with the polymers under a different set of reaction conditions. For example, in general, the reactive groups Y identified above will react under alkaline conditions whereas the N-methylol groupings -Cl-I OR will react under acidic conditions. Because of these factors, the unsymmetrical compounds above are particularly valuable for the step-wise modification of cellulosic textiles.

Other unsymmetrical polyfunctional compounds included by generic formulae I and II are compounds wherein the radical Q and D contain a reactive grouping other than such as, for example, a grouping represented by the structural formula NCOY wherein the reactivity differs from that of the Nson' grouping.

Monofunctional compounds included among the compounds represented by formula I which contain groups capable of imparting desirable properties to polymers which are reacted with the sulfonamide compounds are represented by the structural formula: VII.

wherein Y and R have the same meaning previously given above, and

R is a member selected from the group consisting of substituted and unsubstituted aliphatic hydrocarbon groups containing, for example, from eight to about 20 carbon atoms. Hydrophobic substituents such as fluoroalkyl groups of the formula II' I 'J wherein n has a value of 8 to 20 and x has a value of 2 to 41, are particularly valuable for the chemical modification of cellulosic textiles in order to impart water repellency.

Further monofunctional compounds included among the compounds represented by formula II are heterocyclic compounds represented by the structural formula:

VIII.

GIL-R3 wherein Y and R have the meaning previously given above and x and w are integers with a value of l to 3.

The group X which forms a part of the terminal grouping of certain of the sulfonamides of the present invention is defined as the conjugate base of a Lowry- Bronsted acid and has a dissociation constant in water between 5 X 10' and 5 X 10 and includes polar residues derived from a reagent of weak nucleophilic charactcr.

Included and illustrative of these polar residues but non-limiting thereof are the following groupings:

Sulfate OSO,M Thiosulfate SSO;M F ormate OCOH Pyridinium s s Benzyldimethyl ammonium CH3 N C H 2 C 0H5 Acyl R CO- where R contains one to five carbon atoms, e.g. acetate -OCOCH propionate -OCOC I-I wherein M is an alkali metal, e.g. Na, K, Li, or ammonium.

Illustrative of the sulfonamide compounds of the present invention and included by the various formulae defined above are the following:

CH OCH CH SO NHCH NHSO CH CH OCH CH OCOCH CH SO NH(CH NHSO CH C- H- OCOCH,

(lhOFlhCllrS OzN C1130 L 11201128 OsN NaO SoCH CH sO NHCH OH CH -CHSO N HC H C1130 (.IIzUlIzSOzN 10 pounds of the present invention and not limiting in the scope thereof. It is understood that the various substituent groupings can be substituted one for another into the various generic formulae I through VIII to obtain the novel compounds of the present invention.

Compounds of the present invention may be prepared in one of several reactions as determined by the particular structure of the desired compounds. Illustrative of the reactions which are generally suitable for the preparation of sulfonamide compounds is the reaction of a sulfonyl chloride with an amine represented by the reaction 1: I

wherein Y, R and 0 have the meanings previously ascribed to them.

Heterocyclic compounds can be prepared in a similar manner by employing a heterocyclic amine as illustrated by the equation:

ClCIIgGHgS OgN Further illustrating the basic reaction between the sulfonyl chloride and a diamine is the following equation:

The reaction illustrated in the foregoing equations is generally suitable for the preparation of compounds of formulae III, IV, VII and VIII.

An alternative method for the preparation of these compounds employs carbyl sulfate as shown in reaction 2.

2. Carbyl sulfate amine Illustrative of this basic reaction is that of p'ipcrazine with carbyl sulfate:

(llz-(lllg (3ll'z(3llg() I llN Nll+ l ('llz(,'llz SOz-OSO2 clr mn mlio sovmou som Nso tmcmoso xm CITr-(Hz Unsymmetrical compounds containing the N- methylol group are preferably prepared by reaction of a suitable sulfonamide with formaldehyde as shown inreaction 3.

YSOzTIIII HCHO YSOzNUHqOH R R l ROII YSOzlII-(lIgOR The symmetrical aliphatic compounds of Formula [II can also be prepared by the reaction of a sulfonamide with formaldehyde as shown below:

my-sogxn H0110 YSOzN-(TII NSO Y 1'. I. 1'.

Similarly, the trifunctional compounds of Formula V can also be prepared from a sulfonamide and formaldehyde under suitable conditions as illustrated by the equation below:

/CH7 YSOzfIIH HCIIO YSOzN N-SOzY R CH2 CH2 1T1 SO:

Although the conditions of reaction employed in the methods of preparation illustrated above can vary, it is generally preferred that the reaction between the sulfonyl chloride and the amino (equation 1) take place at a low temperature, usually below C, in the presence of an acid acceptor compound such as a tertiary amino. It is further desirable to employ an inert solvent or diluent in order to aid in cooling the reaction. When the desired monomeric product is unsaturated, a polymerization inhibitor should be used. If, on the other hand, a polymer is desired then reactions involving unsaturated compounds may be run at higher temperatures and omitting the polymerization inhibitor.

Reaction 2 takes place under conditions that can be considerably varied. Temperature ranges are not narrowly critical although generally care must be exercised in selecting reaction conditions for specific compounds since the rate of reaction of the amine with the carbyl sulfate in part depends on the structure of the amine used. lnert solvents may be used for cooling the reaction. Additionally, a polymerization inhibitor is used if the desired product obtained from the reaction, is unsaturated.

The reaction conditions for the reaction 3 between formaldehyde and the sulfonamide are determinative of whether the N-methylol compounds of Formula IV are formed or the trifunctional perhydrotriazine compounds of Formula V are formed. When mild alkaline conditions are used in the presence of water the N- methylol compounds of Formula VI are formed whereas if the reaction conditions are strongly acidic the perhydrotriazine compounds will be formed.

Other methods of preparation can be employed in addition to the direct method by employing a sulfonyl chloride of suitable structure or an amide of suitable structure as illustrated in reaction 3. For example, the following equations illustrate some of the reactions that may be used to make the sulfonamide compounds of the present invention.

The following examples are illustrative of the present invention in that they show the preparation of representative sulfonamide compounds. It is to be understood that these examples are for purposes of illustration only and are not considered limiting of the invention in any way. The sulfonamide compounds of the present invention can be prepared by anyone of the methods described in the following examples.

EXAMPLE I bis (vinylsulfonyl) piperazine A solution of 2-chloroethanesulfonyl chloride (136.8g: 0.84 mole) in 300 ml tetrahydrofuran was slowly added to a stirred solution of recrystallized piperazine (33.6g: 0.39 mole) and triethylamine (169.5 g. 1.68 mole) in 900 ml of tetrahydrofuran at C over a period of 2.5 hours. The temperature of the mixture was slowly allowed to rise to room temperature and stirring was continued for several hours. The solid was removed by filtration, washed with three 500 ml portions of water and dried. The crude product (53.6g; 52.6 percent purity by one hour vinyl analysis (determined by the dodecyl mercaptan method described in the CHEMISTRY OF ACRYLONITRILE, The American Cyanamid Co., Second Ed., NY. 1959, p. 61) using dodecyl mercaptan method) was recrystallized from acetonitrile and 31.0 g. (29.9 percent of theory) of product, m.p. 204.0205.5 C was obtained. The purity of the product by one hour vinyl analysis (dodecyl mercaptan method) was 88 percent.

EXAMPLE ll bis (Z-methoxyethanesulfonyl piperazine A solution of 25 percent sodium methylate (59.6 g.; 0.276 mole) in 200 ml of methanol was slowly added to a stirred mixture of bis (vinylsulfonyl) piperazine (46.06 g.; 0.173 mole) and lOO ml of methanol over a period of one hour at room temperature. The mixture was stirred overnight, filtered and dried. The crude product obtained (52.8 g.; 92.6 percent yield) melted WWWiiiiii1illlllllllll11111111....

at 145.0147.0 and contained 1.7 percent vinyl as determined by the 'dodecyl mercaptan method. Recrystallization from isopropanol gave 31.1 g. of white needles. M.p. l46.0 147.0 C.

Analysis: 1 C N C11 0 Calculated for C,,,H ,N,S,O 19.41 8.48 18.79 Found: 20.00 8.49 21.79

EXAMPLE lll 1,4-bis-(vinylsulfonyl)-2,5-dimethyl piperazine A solution of 2,5-dimethyl piperazine (32.2 g., 0.31 m.; 80 percent trans-20 percent cis), triethylamine (131 g., 1.30 m.) and hydroquinone (0.5 g.) in acetone (1,000 ml.) was chilled to C. 2-chloroethylsulfonyl chloride (106 g., 0.65 m.) was added to the solution dropwise with vigorous stirring while maintaining the internal temperature at l0 to' l5 C. When the addition was complete, the solution was allowed to stir 2 hrs. while warming to room temperature and then left overnight.

Triethylamine hydrochloride (188 g., calc. 178 g.) was removed by filtration and the filtrate stripped of solvent at reduced pressure. The product was obtained as an oily syrup which was taken up in benzene and crystallized by the addition of hexane. The bis-vinyl sulfonamide was obtained in chunky, colorless crystals, m.p. l45158 C (40.7 g., 44 percent yield). The infrared spectrum of the product (CHCl solution) showed maxima at 7.48 and 8.72 (S0 and 10.32;]. (vinyl).

This sample was fractionally crystallized from benzene-hexane to give a sparingly soluble isomer A and a more soluble isomer B whose properties are summarized in the table.

isomer Vinyl Dioxane m. .(.C.) Analysis Solubility A l56-169 18.15% nil B 112 114 18.35% About 30% Calculated value: 18.35%.(Determined by the dodocyl mercaptan method described in THE CHEMISTRY OF-ACRYLONITRILE. The American Cyanamid 0)., Second Edi, NY. 1959, p.61.)

Calc. 38.56 5.75 9.99 22.80 Found: 38.93 6.30 10.38 24.72

Example V 1,4-bis-(2-methoxyethyl sulfonyl)-2-methylpiperazine 2-methylpiperazine (14.0 g., 0.14 m.) and triethylamine (28.5 g., 0.28 m.) were dissolved in chloroform (84 ml.) and added dropwise during one-half hour to a solution of 2-methoxy-ethylsulfonyl chloride (50 g., 0.315 m.) and hydroquinone (0.05 g.) in benzene (112 ml.) while maintaining the reaction temperature at 0-5 C. with cooling. At the completion of the addition, the reaction mixture was permitted to stir one-half hour at 5 C, warmed to room temperature and filtered free of triethylamine hydrochloride (38.4 g., calc. 38.4 g.). The solvents were removed in vacuo to give the product as an amber syrup (48.3 g.). The product was purified for analysis by crystallization from benzeneheirane to give colorless crystals, m.p. 808 1.

Analysis C H N S Calc. 38.35 7.25 8.13 18.61

, Found: 39.27 7.17 8.53 19.02

Example V1 Elemental Analysis c H N s Calculated for 4 c,,,1-|,,N,o.s, 40.79 6.16 9.51 21.78 7 Found: lsomer A 40.56 7.14 9.20 21.30 Found: isomer B 40.58 6.27 9.30 21.64

EXAMPLE 1V 1,4-bin-(vinylsulfonyl)-2-methylpiperazine A solution of Z-methylpiperazine (93 g., 0.93 m;) triethylamine (395 g., 3.92 m.) and hydroquinone (3 g.) in acetone (3,500 ml.) was chilled to l0 C. 2-chloroethylsulfonyl chloride (319 g., 1.96 m.) was added to the solution dropwise with vigorous stirring while maintaining the internal temperature at l0 C. When the addition was complete, the solution was stirred at -10 for 1 hour, permitted to warm to room temperature and left overnight.

Triethylamine hydrochloride (569 g., calc. 540 g.) was removed by filtration, and the filtrate was stripped of solvent to give. the crude bis-vinylsulfonamide (320 g.) as an oily residue. Crystallization from benzenehexane gave white prisms, m.p. 1l2-114 C. (65 g., 25 percent yield). This sample showed 19.05 percent vinyl (calc. 19.3 percent) by the dodecyl mercaptan method. lts infrared spectrum (Ci-1C1 solution) showed maxima at 7.45 and 8.70 and 10.32;; (vinyl). A recrystal-' lized sample was submitted for elemental analysis: Anal. C H N S l-(3-methoxypropionyl)-4-(vinylsulfonyl) piperazine l-(3-methoxypropionyl) piperazine (17.2 g., 0.1 m.)

was dissolved in water (250 ml.) containing potassium bicarbonate (22 g., 0.22 m.). The solution was cooled to 5 C. and 2-chloro-ethylsulfonyl chloride (17.9 g.,

Analysis C H N Cale. 45.7 6.84 10.65 Found: 45.07 7.18 10.38

EXAMPLE VII N-methylvinylsulfonamide- I .Z-chloroethylsulfonyl chloride (163 g., 1.0 m.) and V hydroquinone (1 g.) were dissolved in N,N'-dimethylformamide (500 ml.) and the resulting solution cooled to 40 C. Methyl amine (93.2 g., 3.0 m.) was added as a gas while maintaining the reaction temperature at 40 to 50 C. The reaction was permitted to stir while warming to room temperature. Methylamine hydrochloride was removed by filtration and the filtrate was fractionally distilled in vacuo to give N-methylvinyl sulfonamide as a yellow liquid, b.p. 104108 C.

(0.1-0.2mm.) in 39 percent yield. The product has a refractive index at 26 C. of 1.4702 and a purity of 85 percent as determined by vinyl analysis.

A redistilled sample was analyzed:

Analysis C H N S Calcd. 29.88 5.78 11.57 26.40 Found 29.53 5.96 11.62 26.26

Example VIII l,3, 5,-tris-(vinylsulfonyl) hexahydro-1-3-5 triazine Vinyl sulfonamide (27 g., 0.25 m.), formaldehyde (37 percent aqueous, 20.3 g., 0.25 m.) and sulfuric acid (0.4 g.) were dissolved in water (10 ml.) and heated to gether at 77 C for 5 hours. The mixture was cooled to room temperature, diluted with water, and the pH adjusted to 5.5. The solution was extracted with chloroform and the product recovered by evaporation of the organic solvent. The triazine (12.8 g., 43 percent yield) was recovered as a pale yellow syrup whose purity was found to be 94 percent as determined by vinyl analysis.

The infrared spectrum (CI-ICl solution) of the product showed maxima at 7.50, and 8.73 (S0,) and 10.33

1. (vinyl).

EXAMPLE IX The compounds illustrated in the foregoing examples as well as those compounds included in Formulae I to VIII set forth above are valuable intermediates for various purposes, particular chemical synthesis, and as monomers for the formation of polymers and further, have utility in the therapeutic field. More importantly, they are particularly useful as reagents for the chemical modification of polymers and especially so for the crosslinking and chemical modification of cellulosic textile materials. For example, the grouping has excellent reactivity toward hydroxyl groups in the presence of alkaline catalysts and polyfunctional compounds such as those shown in Formulae III, IV and V, are excellent crosslinking agents for cellulosic textiles and impart desirable properties thereto such as improved resilience and dimensional stability which are particularly important in the textile field.

Unsymmetrical polyfunctional compounds such as those shown in Formula VI can be employed to crosslink polymers containing active'hydrogen atoms in a stepwise process. For example, the initial reaction between a cellulosic textile and a compound of Formula VI can be achieved by carrying out the reaction in the presence of alkaline catalysts. Subsequently the remaining grouping can be reacted with the cellulosic textile material by changing the reaction conditions and employing an acidic catalyst sufficient to lower the pH below 7.

In addition to being useful for the crosslinking of various polymeric materials containing active hydrogen atoms, the sulfonamide compounds of the present invention are also useful for introducing other modifying groups into polymers and are particularly interesting for their wide applicability in the textile field. For example, if the monofunctional compounds such as are included in Formulae VII and VIII contain terminal groupings that are hydrophobic or oil repellent, textiles can be treated therewith in order to impart these properties to the textile.

What is claimed is:

l. A compound of the formula:

YSOzN NS OzY CH CH2 N isozY wherein Y and Y are members selected from the group consisting of R and R are members selected from the group consisting of hydrogen and lower alkyl, and

X is a polar residue derived from a reagent of weak nucleophilic character, said polar residue selected from the group consisting of Sulfate OSO M Thiosulfate SSO,M Formate OCOH Pyridinium -NC II Benzyldimethyl ammonium N C IIzC 5H5 -OCOR where R:, contains one to five carbon atoms,.and wherein M is Na, K, Li, or ammonium. 2. 

